CN113786864A - Catalyst and method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation by using same - Google Patents
Catalyst and method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation by using same Download PDFInfo
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- valerolactone
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 130
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229940040102 levulinic acid Drugs 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 20
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 4
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 4
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910021012 Co2(CO)8 Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910016660 Mn2(CO)10 Inorganic materials 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- QFEOTYVTTQCYAZ-UHFFFAOYSA-N dimanganese decacarbonyl Chemical compound [Mn].[Mn].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] QFEOTYVTTQCYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910018385 Mn(CO)5 Inorganic materials 0.000 claims description 3
- 229910017333 Mo(CO)6 Inorganic materials 0.000 claims description 3
- 230000002051 biphasic effect Effects 0.000 claims description 3
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical compound [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019813 Cr(CO)6 Inorganic materials 0.000 claims description 2
- 229910017147 Fe(CO)5 Inorganic materials 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003446 ligand Substances 0.000 abstract description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940094933 n-dodecane Drugs 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYFPSYVVFFFYBF-UHFFFAOYSA-N sodium;triphenylphosphane Chemical compound [Na].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VYFPSYVVFFFYBF-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Abstract
The invention relates to a catalyst and a method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation by using the catalyst, and belongs to the technical field of biomass catalysis. Consists of a metal carbonyl compound, preferably Ru, and a base3(CO)12Or Mo (CO)6The base is preferably KOH or K2CO3The molar ratio of the metal carbonyl compound to the metal carbonyl compound is 1: 5-500. The catalyst system is suitable for a high-pressure reaction kettle reactor equipped with magnetic stirring or mechanical stirring to react in a liquid medium, wherein the liquid medium is preferably toluene, water and a toluene-water two-phase solvent system. The catalyst system has easily obtained raw materials, does not need to use a phosphine ligand, can efficiently catalyze levulinic acid to prepare the gamma-valerolactone by hydrogenation under mild conditions, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of biomass catalysis, and particularly relates to a catalyst and a method for preparing gamma-valerolactone by catalyzing levulinic acid to be hydrogenated by the catalyst.
Background
Levulinic Acid (LA) is one of the most important platform molecules and can be prepared by hydrolyzing cheap and abundant biomass resources such as cellulose and the like under an acidic condition. A series of industrial chemicals and biofuels can be prepared from levulinic acid through processes of catalytic hydrogenation, esterification or oxidation and the like. Gamma-valerolactone, one of the hydrogenation products of levulinic acid, not only can be used as a green solvent, a food and a fuel additive, but also can be used as a raw material for preparing high-energy density liquid fuel and high value-added chemicals. The development of a catalyst capable of efficiently catalyzing levulinic acid hydrogenation to prepare gamma-valerolactone is the key point for realizing the effective preparation of gamma-valerolactone from biomass.
In the reaction process of catalyzing levulinic acid to prepare gamma-valerolactone by hydrogenation, a ruthenium-based catalyst system consisting of phosphine ligands is typical. In 1982, Ikariya et al (J. organomet. chem., 1982, 231, 79-90) used RuCl2(PPh3)3As the catalyst, the molar ratio of the catalyst to the levulinic acid is 1: 200, and the H is 1.2 MPa2And the reaction is carried out for 24 hours at 180 ℃, and the yield of the gamma-valerolactone reaches 99 percent. In 2008, Horvath et al (Top Cat., 2008, 48, 49-54) used Ru (acac)3The catalyst system is/10 TPPTS (TPPTS: triphenylphosphine sodium tri-meta-sulfonate) and the molar ratio of the catalyst to the levulinic acid is 1: 600 and 6.9 MPa H2And the reaction is carried out for 12 hours at 140 ℃, and the separation yield of the gamma-valerolactone reaches 95 percent. In 2009, Fu et al (Angew. chem. int. Ed., 2009, 48, 6529-3·3H2O/3 PPh3100 KOH (or NaOH, NEt)3Pyridine, etc.) as a catalyst system, and formic acid which is a byproduct of cellulose hydrolysis as a hydrogen source, and reacting for 6 or 12 hours at the molar ratio of the catalyst to the levulinic acid of 1: 1000 and the temperature of 150 ℃, wherein the yield of the gamma-valerolactone is 67-94%. In 2012, Zhou et al (Green chem., 2012, 14, 2388-2Cl2]2/3 1,5-P t Bu2-py/2400 KOH as catalyst system in a catalyst to levulinic acid molar ratio of 1: 2000, 5.0 MPa H2And the reaction is carried out for 15 hours at 100 ℃ and the like, and the yield of the gamma-valerolactone reaches 96 percent.
The phosphine ligand is sensitive to moisture and air, so that the life cycle is short and the preparation is difficult; in addition, the phosphine ligand is easy to cause pollution when entering the environment. Aiming at the existing catalyst for catalyzing levulinic acid hydrogenation to prepare gamma-valerolactone, which needs to use a phosphine ligand, the invention provides a catalyst system which has mild reaction conditions, high catalytic activity and no need of using the phosphine ligand.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the catalyst and the method for preparing the gamma-valerolactone by catalyzing the hydrogenation of the levulinic acid have the advantages that the raw materials of the catalyst system are easy to obtain, a phosphine ligand is not needed, the gamma-valerolactone can be prepared by efficiently catalyzing the hydrogenation of the levulinic acid under mild conditions, and the catalyst has good industrial application prospect.
The technical scheme adopted by the invention is as follows:
the catalyst consists of a metal carbonyl compound and alkali, wherein the molar ratio of the metal carbonyl compound to alkali molecules is 1: 5-500 calculated by the number of metal atoms in the metal carbonyl compound.
Further, the metal carbonyls include, but are not limited to, Rh6(CO)16、Ru3(CO)12、Co2(CO)8、Mn2(CO)10、Mo(CO)6、Fe(CO)5、Cr(CO)6、Mn(CO)5Br、Re(CO)5One kind of Br.
Further, the metal carbonyl compound is preferably Ru3(CO)12Or Mo (CO)6。
Further, the base includes, but is not limited to, KOH, NaOH, LiOH, K2CO3、KHCO3、(COOK)2、KCl、NaOMe、KOMe、NaOEt、KOEt、t-BuONa、t-BuOK、NEt3One of them.
Further, the base is preferably KOH or K2CO3。
A method for preparing gamma-valerolactone by hydrogenation of levulinic acid under catalysis of a catalyst comprises the following steps: under the hydrogen atmosphere, the initial hydrogen pressure is within the range of 1-100 bar, under the temperature condition of 20-160 ℃, the metal carbonyl compound and levulinic acid substrate molecules react in a liquid medium according to the molar ratio of 1: 500-200000, stirring is carried out in the reaction, and the reaction time is 0.1-100 hours, so that the product gamma-valerolactone is obtained.
Further, the liquid medium comprises one or more of but not limited to toluene, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, methanol, ethanol, isopropanol and water, and the dosage is 1-1000 mL.
Further, the liquid medium is preferably toluene, water and a toluene-water biphasic solvent system.
Furthermore, magnetic stirring or mechanical stirring is adopted for stirring, and the stirring speed is 100-800 revolutions per minute.
The invention has the beneficial effects that: the invention provides a catalyst system which can effectively catalyze levulinic acid to prepare gamma-valerolactone by hydrogenation under mild conditions without using phosphine ligand, and the catalyst system has the advantages of easily available raw materials, simple composition, good repeatability, low environmental pollution, high catalytic activity, low cost and good industrial application prospect.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention.
The gamma valerolactone yield in the present invention was analyzed using a gas chromatograph equipped with a hydrogen ion flame detector.
Example one
Weighing 1.10 mg Ru3(CO)120.71 g of levulinic acid (levulinic acid: Ru =1000:1 (molar ratio)) was put in a 25mL reaction vessel, and the vessel body was assembled. The atmosphere in the autoclave was replaced with nitrogen, 2mL of toluene was added by a syringe under nitrogen protection, and then the atmosphere in the autoclave was further replaced with hydrogen and charged with hydrogen to 50 bar. The kettle was placed in a heating device and heated to 120 ℃ and maintained at this temperature for 16 h. After the reaction is finished, the temperature of the kettle body is quickly reduced to 5 ℃, and the residual hydrogen in the kettle is removed. The solvent and water generated during the reaction were removed from the resulting reaction mixture under reduced pressure, and 1mL of toluene and 20. mu.L of n-dodecane were further added thereto, and the mixture was stirred uniformly and analyzed by Gas Chromatography (GC) (RB-Wax column 30 m. times.0.32 mm. times.0.5. mu.m), and the yield of γ -valerolactone was 44%.
Example two
In the same experimental procedure as in example one, the metal carbonyl was converted to Co2(CO)8(0.88 mg), the yield of gamma-valerolactone was 13%.
EXAMPLE III
In the same experimental procedure as in example one, the metal carbonyl was converted to Mn2(CO)10(1.01 mg), the yield of gamma-valerolactone was 8%.
Example four
In the same experimental procedure as in example A, the metal carbonyl was converted to Mo (CO)6(1.36 mg), the yield of gamma-valerolactone was 39%.
EXAMPLE five
In the same experimental procedure as in example one, the metal carbonyl was converted to Mn (CO)5Br (1.42 mg), yield of gamma-valerolactone was 11%.
TABLE I, EXAMPLES I TO V Overall results of hydrogenation of levulinic acid catalyzed by metal carbonyl compounds
| Numbering | Catalyst and process for preparing same | Gamma valerolactone yield/% |
| Example one | Ru3(CO)12 | 44 |
| Example two | Co2(CO)8 | 13 |
| EXAMPLE III | Mn2(CO)10 | 8 |
| Example four | Mo(CO)6 | 39 |
| EXAMPLE five | Mn(CO)5Br | 11 |
As can be seen from Table I, Ru is selected as the metal carbonyl compound in the catalyst3(CO)12And Mo (CO)6The yield of gamma-valerolactone was the best.
EXAMPLE six
Weighing 1.10 mg Ru3(CO)12、0.0681 g K2CO30.71 g of levulinic acid (levulinic acid: K)2CO3Ru =1000: 100: 1 (molar ratio)) was placed in a 25mL reaction vessel, and the vessel body was assembled. The atmosphere in the autoclave was replaced with nitrogen, 2mL of toluene was added by a syringe under nitrogen protection, and then the atmosphere in the autoclave was further replaced with hydrogen and charged with hydrogen to 50 bar. The kettle was heated to 100 ℃ in a heating apparatus and maintained at this temperature for 1 h. After the reaction is finished, the temperature of the kettle body is quickly reduced to 5 ℃, and the residual hydrogen in the kettle is removed. The solvent and water generated during the reaction were removed from the resulting reaction mixture under reduced pressure, and 1mL of toluene and 20. mu.L of n-dodecane were further added thereto, and the mixture was stirred uniformly and analyzed by Gas Chromatography (GC) (RB-Wax column 30 m. times.0.32 mm. times.0.5. mu.m), and the yield of γ -valerolactone was 100%.
EXAMPLE seven
In the same six experimental procedures as in example, the base was changed to KOH (0.0276 g), and the yield of gamma-valerolactone was 100%.
Example eight
In the same manner as in the six experimental steps of example, the alkali conversion was changed to NaOH (0.0197 g), and the yield of gamma-valerolactone was 99%.
Example nine
In the same six experimental procedures as in example, the base was changed to LiOH (0.0118 g), and the yield of gamma-valerolactone was 96%.
Example ten
In the same experimental procedure as in example six, the alkali was changed to KHCO3(0.0493 g), the yield of gamma-valerolactone was 98%.
EXAMPLE eleven
Same as the six experimental procedures of example, alkali transformation is (COOK)2(0.0819 g), the yield of gamma-valerolactone was 89%.
Example twelve
In the same procedure as in the six experimental procedures of example, the base shift was KCl (0.0367 g), and the yield of gamma-valerolactone was 17%.
EXAMPLE thirteen
In the same procedure as in the six experimental procedures of example, base shift was performed to NEt3(0.0498 g), the yield of gamma-valerolactone was 89%.
TABLE II, examples six to thirteen Ru3(CO)12Integrated results of catalytic levulinic acid hydrogenation
| Numbering | Alkali | Gamma valerolactone yield/% |
| EXAMPLE six | K2CO3 | 100 |
| EXAMPLE seven | KOH | 100 |
| Example eight | NaOH | 99 |
| Example nine | LiOH | 96 |
| Example ten | KHCO3 | 98 |
| EXAMPLE eleven | (COOK)2 | 89 |
| Example twelve | KCl | 17 |
| EXAMPLE thirteen | NEt3 | 89 |
As can be seen from Table II, the base in the catalyst is selected from KOH or K2CO3The yield of gamma-valerolactone was the best.
Example fourteen
Same as example six Experimental procedure, K2CO3The mass was changed to 0.0068 g, and the yield of γ -valerolactone was 66%.
Example fifteen
Same as example six Experimental procedure, K2CO3The mass was changed to 0.0136 g, and the yield of γ -valerolactone was 83%.
Example sixteen
Same as example six Experimental procedure, K2CO3The mass was changed to 0.0341 g, and the yield of γ -valerolactone was 89%.
Example seventeen
Same as example six Experimental procedure, K2CO3The mass was changed to 0.1362 g, and the yield of gamma-valerolactone was 74%.
TABLE III, EXAMPLE VI, EXAMPLE fourteen to EXAMPLE seventeen Ru3(CO)12Integrated results of catalytic levulinic acid hydrogenation
| Numbering | n(K2CO3)/n(Ru) | Gamma valerolactone yield/% |
| Example fourteen | 10 | 66 |
| Example fifteen | 20 | 83 |
| Example sixteen | 50 | 89 |
| EXAMPLE six | 100 | 100 |
| Example seventeen | 200 | 74 |
From the table III, when the molar ratio of the alkali molecules to the metal carbonyl compound is increased to 100 according to the number of metal atoms in the metal carbonyl compound, the yield of the gamma-valerolactone is gradually increased; when the molar ratio of the alkali molecules to the metal carbonyl compound exceeds 100, the yield of the gamma-valerolactone is in a descending trend under the condition of continuously increasing. It can be seen that when the molar ratio of the alkali molecule to the metal carbonyl compound is 100, the yield of gamma-valerolactone reaches the best 100%.
EXAMPLE eighteen
In the same procedure as in the sixth experimental step of example, the liquid medium was changed to water (2 mL), and the yield of gamma-valerolactone was 96%.
Example nineteen
In the same six experimental procedures as in example, the liquid medium was changed to a toluene-water two-phase solvent system (1 mL +1 mL), and the yield of gamma-valerolactone was 100%.
Example twenty
In the same manner as in the sixth experimental procedure of example, the liquid medium was changed to tetrahydrofuran (2 mL), and the yield of gamma-valerolactone was 92%.
Example twenty one
In the same experimental procedure as in example six, the liquid medium was changed to ethanol (2 mL) and the yield of gamma-valerolactone was 46%.
TABLE IV, EXAMPLE VI, EXAMPLE eighteen to EXAMPLE twenty-one Ru3(CO)12Integrated results of catalytic levulinic acid hydrogenation
| Numbering | Liquid medium | Gamma valerolactone yield/% |
| EXAMPLE six | Toluene | 100 |
| EXAMPLE eighteen | Water (W) | 96 |
| Example nineteen | Toluene + Water (1: 1) | 100 |
| Example twenty | Tetrahydrofuran (THF) | 92 |
| Example twenty one | Ethanol | 46 |
As can be seen from Table IV, when the liquid medium in the reaction is toluene, water, a toluene + water biphasic solvent and tetrahydrofuran, the yield of gamma-valerolactone is high.
Example twenty two
In the same procedure as in the sixth experimental procedure of example, the reaction temperature was changed to 80 ℃ and the yield of gamma-valerolactone was 81%.
Example twenty three
In the same manner as in the six experimental procedures of example, the reaction temperature was changed to 60 ℃ and the reaction time was changed to 4 hours, whereby the yield of gamma-valerolactone was 23%.
Example twenty-four
In the same six experimental procedures as in example, the hydrogen pressure was changed to 10 bar, and the yield of gamma-valerolactone was 97%.
Example twenty-five
In the same six experimental procedures as in example, the reaction temperature was changed to 80 ℃, the hydrogen pressure was changed to 10 bar, the reaction time was changed to 8 hours, and the yield of gamma-valerolactone was 99%.
Example twenty-six
Same as example six Experimental procedure, Ru3(CO)12The mass was changed to 0.44 mg, K2CO3The mass was changed to 0.0272 g, and the mass of levulinic acid was changed to 1.42 g (levulinic acid: K)2CO3Ru = 5000: 100: 1 (molar ratio)), the reaction time was changed to 4h, and the γ -valerolactone yield was 99%.
Example twenty-seven
In the same twenty-six experimental procedures as in example, the reactor volume was changed to 500mL, the hydrogen pressure was changed to 100bar, the reaction time was changed to 16h, the reaction temperature was changed to 120 ℃, the toluene volume was changed to 40 mL, and the mass of levulinic acid was changed to 28.4 g (levulinic acid: K)2CO3Ru = 100000: 100: 1 (molar ratio)), the γ -valerolactone yield was 82%.
TABLE V, EXAMPLE twenty two to EXAMPLE twenty seven Ru3(CO)12Integrated results of catalytic levulinic acid hydrogenation
| Numbering | Levulinic acid, base, Ru (molar ratio) | Reaction temperature (C)oC） | Hydrogen pressure (bar) | Reaction time (h) | Gamma valerolactone yield/% |
| Example twenty two | 1000 : 100 :1 | 80 | 50 | 1 | 81 |
| Example twenty three | 1000 : 100 :1 | 60 | 50 | 4 | 23 |
| Example twenty-four | 1000 : 100 :1 | 100 | 10 | 1 | 97 |
| Example twenty-five | 1000 : 100 :1 | 80 | 10 | 8 | 99 |
| Example twenty-six | 5000 : 100 :1 | 100 | 50 | 4 | 99 |
| Example twenty-seven | 100000 : 100 :1 | 120 | 100 | 16 | 82 |
It can be seen from table five that the reaction for catalyzing the hydrogenation of levulinic acid to gamma valerolactone is comprehensively related to the reaction temperature, the hydrogen pressure, the reaction time and the molar ratio between levulinic acid and the catalyst of the invention.
The catalyst system for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid, which is provided by the invention, has the advantages of mild reaction conditions, high catalytic activity and no need of using phosphine ligand, is suitable for a high-pressure reaction kettle reactor equipped with magnetic stirring or mechanical stirring, and has the advantages of easily available raw materials, simple composition, good repeatability and good industrial application prospect.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. The present invention is not limited to the above-described embodiments, which are described in the specification and illustrated only for illustrating the principle of the present invention, but various changes and modifications may be made within the scope of the present invention as claimed without departing from the spirit and scope of the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A catalyst, characterized by: the metal carbonyl compound and alkali are used in a molar ratio of 1: 5-500, calculated by the number of metal atoms in the metal carbonyl compound.
2. A catalyst as claimed in claim 1, wherein: the metal carbonyl compounds include but are not limited to Rh6(CO)16、Ru3(CO)12、Co2(CO)8、Mn2(CO)10、Mo(CO)6、Fe(CO)5、Cr(CO)6、Mn(CO)5Br、Re(CO)5One kind of Br.
3. A catalyst as claimed in claim 2, wherein: the metal carbonyl compound is preferably Ru3(CO)12Or Mo (CO)6。
4. A catalyst as claimed in claim 1, wherein: the base includes but is not limited to KOH, NaOH, LiOH, K2CO3、KHCO3、(COOK)2、KCl、NaOMe、KOMe、NaOEt、KOEt、t-BuONa、t-BuOK、NEt3One kind of (1).
5. A catalyst as claimed in claim 4, wherein: the base is preferably KOH or K2CO3。
6. A method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation by using the catalyst as claimed in any one of claims 1 to 5, wherein the method comprises the following steps: the method comprises the following steps: under the hydrogen atmosphere, the initial hydrogen pressure is within the range of 1-100 bar, under the temperature condition of 20-160 ℃, the metal carbonyl compound and levulinic acid substrate molecules react in a liquid medium according to the molar ratio of 1: 500-200000, stirring is carried out in the reaction, and the reaction time is 0.1-100 hours, so that the product gamma-valerolactone is obtained.
7. The method for preparing gamma-valerolactone by hydrogenation of levulinic acid under the catalysis of the catalyst according to claim 6, wherein the method comprises the following steps: the liquid medium comprises one or more of but not limited to toluene, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, methanol, ethanol, isopropanol and water, and the dosage is 1-1000 mL.
8. The method for preparing gamma-valerolactone by hydrogenation of levulinic acid under the catalysis of the catalyst according to claim 7, wherein the method comprises the following steps: the liquid medium is preferably toluene, water and a toluene-water biphasic solvent system.
9. The method for preparing gamma-valerolactone by hydrogenation of levulinic acid under the catalysis of the catalyst according to claim 6, wherein the method comprises the following steps: magnetic stirring or mechanical stirring is adopted for stirring, and the stirring speed is 100-800 revolutions per minute.
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